纯相低氧纳米WC-Co复合粉的制备

以紫钨、四氧化三钴、炭黑为原料,在高真空度条件下利用原位反应合成技术制备出物相纯净、平均粒径约为80 nm的WC-Co复合粉。研究了制备工艺参数对纳米复合粉相组成、粒径、氧含量及最终烧结硬质合金块体材料组织性能的影响。结果表明,纳米复合粉中氧含量较高时,会导致后续烧结过程中发生脱碳反应,使烧结制备的块体材料致密度和力学性能明显下降。将纳米复合粉在800℃下真空热处理2.5 h可有效降低粉末中的氧含量,同时热处理后的粉末颗粒无明显长大,平均粒径为85 nm。向复合粉中加入1.1%TiC与0.9%VC进行SPS烧结,烧结块体平均晶粒尺寸为105 nm,且尺寸分布均匀,致密度达99%以上,硬度(HV30)为21 450 MPa,断裂韧性达到9.81 MPa·m~(1/2)。     

Cr颗粒尺寸对Ni-Cr复合镀层750℃氧化性能的影响

采用复合电镀技术,通过向普通电镀溶液中分别加入平均粒度约40nm和1～5μm Cr粉的方法,在Ni基材上制备了2种金属Ni基纳米Cr粒子弥散的Ni-Cr复合镀层(简称为ENCCs Ni-Cr)和1种微米Cr粒子弥散的Ni-Cr复合镀层(简称为EMCCsNi-Cr).750℃氧化对比实验结果表明:在相同的Cr颗粒含量条件下,Cr颗粒尺寸的减小明显提高了Ni-Cr复合镀层的抗氧化性能;在相同的Cr颗粒含量条件下,Cr颗粒越细,Ni-Cr复合镀层的氧化性能越好.     

Ni/B微纳米复合粒子的制备与性能

采用化学镀镍的方法制备Ni/B微纳米复合粒子。运用TEM、EDS和XRD方法对复合粒子的形貌、组成和物相进行表征,并通过TG-DTA热分析仪和热常数分析仪研究Ni/B微纳米复合粒子的热稳定性和导热系数。结果表明,真空干燥得到的复合粒子为核壳结构,纳米镍的尺寸约为21.7 nm,纳米镍粒子紧密均匀地包裹在硼粉表面,并且镍和硼的质量比为1:1;与原料硼粉相比,复合粒子与空气的反应放热峰提前36 ℃左右,表明纳米镍粒子具有明显的催化效果;同时,复合粒子的导热系数也有所增大     

WC/Co纳米复合粉质量特性的研究

本文探讨了喷雾转换法制备WC/Co纳米复合粉的生产工艺特点、粉末的物理化学特性以及在超细合金中的应用效果。各方面的实验数据表明:WC/Co复合粉中WC碳化完全、粒度细而均匀,钨钴元素达到分子级均匀混合,Co对WC形成纳米级包覆,粉末颗粒外形多呈球状,球体由部分合金化的WC/Co粒子聚合而成,粒子之间存在明显的烧结颈,其亚晶尺寸在100nm以下。复合粉经强化球磨后制取的超细合金较传统工艺制备的合金的WC相晶粒更加均匀,具有更好的物理力学性能和更高的使用寿命。即使不添加抑制剂,复合粉制备的合金仍具有晶粒细而均匀的特点。     

胶束性质对光化学制备金纳米粒子的影响

研究了阴离子表面活性剂疏水链的长度对光化学制备金纳米粒子的影响。结果发现，疏水链越长，获得的金纳米粒子的尺寸越小；特别是苯环的引入使诱导和自催化现象越加不明显。在十二烷基磺酸钠体系中获得的金纳米粒子的λmax位于540．7nm，TEM表征的平均粒径为47．1nm；十二烷基苯磺酸钠体系的λmax位于526．5nm，平均粒径为6．7nm。探讨了胶束性质对光化学制备金纳米粒子的影响。     

Ni-Al2O3纳米复合镀层的氧化性能研究

采用复合电镀技术,通过向普通电镀溶液中加入平均粒度为90nm的Al2O3粉的方法在Ni基材上制备了Ni-Al2O3纳米复合涂层,SEM/EDAX分析表明,Al2O3纳米颗粒不仅均匀分布在Nj纳米晶中,而且还细化了基体Ni的晶粒尺寸.1000℃氧化实验表明:弥散分布在镀层中的Al2O3,纳米粒子并没有明显提高Ni的氧化性,但通过阻碍氧化过程中Ni的外扩散从而改变了NiO膜的形成过程.     

纳米及超细复合粉添加对超粗晶硬质合金晶粒长大的影响及机制

在粗颗粒WC/Co混合粉末中分别添加平均粒径为100、250、400nm的WC-8Co复合粉,经球磨混合压坯后在不同温度进行Ar气保护烧结。针对烧结块体的形貌、晶粒尺寸及其分布进行了研究,并分析了复合粉添加对不同烧结阶段WC晶粒长大的影响机理。研究发现,在WC/Co混合粉中加入纳米和亚微米复合粉末均可制备得到超粗晶硬质合金,且添加纳米复合粉烧结的试样平均晶粒尺寸达到9.3μm。烧结初期,纳米和亚微米复合粉通过增加混合粉末的表面能而有效促进WC晶粒长大;当达到液相烧结温度时,添加纳米复合粉的烧结块体中,由于小晶粒具有更大的溶解驱动力,促使小晶粒溶解并在周围大晶粒表面析出,进一步增大烧结块体的晶粒尺寸;添加亚微米复合粉的块体中,小晶粒WC呈集中分布,使其溶解驱动力较小,且析出主要发生在周围细小晶粒之间,达到溶解析出动态平衡,从而使烧结块体的平均晶粒尺寸增长缓慢。     

氢还原法制备80：20镍银纳米复合粉的研究

以氢氧化钠、六水合硝酸镍、硝酸银为原料，采用化学共沉淀法制备氢氧化镍-氧化银复合粉：然后在封闭循环氢还原炉中还原氢氧化镍．氧化银复合粉，得到银镍复合粉。结果表明：制备氢氧化镍-氧化银复合粉的最佳工艺为，温度25℃，搅拌速度1200dmin，搅拌时间60min，反应终点的pH值13，滴加氢氧化钠溶液的速度为50ml/mim氢氧化镍．氧化银复合粉的粒度为3～45nm；在封闭循环氢还原炉中的还原条件为300℃，30min，镍银复合粉的粒度为2-20nm。     

Cr颗粒尺寸对Ni-Cr复合镀层750℃热腐蚀性能影响

采用复合电镀技术,通过向普通电镀溶液中分别加入平均粒度为40 nm和1~5μm的Cr粉的方法在Ni基材上制备了一种金属Ni基纳米Cr粒子弥散的Ni-Cr纳米复合镀层和一种微米Cr粒子弥散的Ni-Cr复合镀层。混合盐(75 wt%Na2SO4+25wt%NaCl)750℃热腐蚀行为结果表明:与微米Cr粒子弥散的Ni-12.4 wt%Cr复合镀层相比,Ni-11wt%Cr纳米复合镀层表现出更好的耐腐蚀性能。SEM/EDAX、XRD和TEM分析表明,在相同的Cr颗粒含量条件下,Cr颗粒尺寸的降低提高了Ni-Cr复合镀层的抗腐蚀性能,这是因为Cr颗粒尺寸的降低和基体Ni晶粒的细化增加了单位面积内的Cr2O3形核率,缩短不同Cr2O3核间的距离,与此同时基体Ni晶粒的细化有利于保护性氧化物形成元素Cr沿晶界向腐蚀前沿的快速扩散,从而加速了保护性Cr2O3膜的快速形成。     

四方相钛酸钡纳米粉体的特殊液相沉淀法制备

本文通过液相反应胶粒析出机理分析,采用快速高强度机械混合液相复合沉淀法制备了小粒径高度均匀混合的氢氧化氧钛和碳酸钡复合纳米粉体。用TEM和XRD对粉体进行了表征。平均粒径为3．5nm,且分布均匀、疏松的无定形氢氧化氧钛和四方相碳酸钡混合粉体。利用纳米粒子小尺寸效应,在低温800℃条件下焙烧获得了钛酸钡纳米粉体。经TEM和XRD表征结果为平均粒径50nm的四方相钛酸钡纳米粉体。     

The effect of submicron-sized initial tungsten powders on microstructure and properties of infiltrated W-25 wt.% Cu alloys

In the present work, several W-25 wt% Cu alloys have been prepared through combined processes of high-energy ball-milling, liquid-phase sintering and infiltration, using the precursors of industrial copper powders with an average particle size of 50 μm and tungsten powders with alternative average particle size of 8 μm, 800 nm, 600 nm or 400 nm. Microstructure characteristics, relative density, hardness and electrical conductivity of the WCu alloys were investigated to elucidate the effect of initial particle size of tungsten powders. EBSD was further utilized to reveal the orientation and grain size distribution in the WCu alloys prepared by 8 μm and 400 nm-sized tungsten powders. The results showed that the WCu alloy made by 400 nm-sized tungsten powders exhibited excellent homogeneity for both sintered tungsten powders and grains, together with the highest relative density of 98.9%, the highest hardness of 230 HB, and good electrical conductivity of 48.7% IACS. Moreover, it also showed highly improved arc erosion and mechanical wear resistances.     

Preparation of ultrafine tungsten powders by in-situ hydrogen reduction of nano-needle violet tungsten oxide

Ultrafine tungsten powders with a grain size below 0.5 μm are key raw materials for fabricating ultrafine cemented carbides. Conventional hydrogen reduction technique has been utilized to prepare the ultrafine tungsten powders. In the present work, highly pure nano-needles of violet tungsten oxide (WO_2.72) were reduced by dry hydrogen. Nucleation and growth of the metallic tungsten in the early stage of hydrogen reduction have been studied by XRD, FESEM and HRTEM. Mechanism of formation of nano-size tungsten powders is proposed and a concept of in-situ hydrogen of the nano-needle WO_2.72 is presented. Empirical relations between an average diameter of nano-needle WO_2.72 and an average particle size of the resultant tungsten powders in both stage of nucleation and industrial conduction have been established. These empirical relations could be a reasonable guidance for suitably choosing the raw materials of nano-needle WO_2.72 to prepare ultrafine tungsten powders. It has been determined that the BET special surface areas of the in-situ hydrogen-reduced tungsten powders with the average particle size of 0.2 μm and 0.3 μm, which were produced from the raw nano-needle WO_2.72 powders with the average diameter of 60 nm and 80 nm, are 6.03 m²/g and 4.65 m²/g, and the oxygen contents are 0.35% and 0.29%, respectively.     

Microstructure and properties of liquid-phase sintered tungsten heavy alloys by using ultra-fine tungsten powders

The microstructure and properties of liquid-phase sintered 93W-4.9Ni-2.1Fe tungsten heavy alloys using ultra-fine tungsten powders (medium particle size of 700 nm) and original tungsten powders (medium particle size of 3um) were investigated respectively. Commercial tungsten powders (original tungsten powders) were mechanically milled in a high-energy attritor mill for 35 h. Ultra-fine tungsten powders and commercial Ni, Fe powders were consolidated into green compacts by using CIP method and liquid-phase sintering at 1465℃ for 30 rain in the dissociated ammonia atmosphere. Liquid-phase sintered tungsten heavy alloys using ultra-fine tungsten powders exhibit full densification (above 99% in relative density) and higher strength and elongation compared with conventional liquidphase sintered alloys using original tungsten powders due to lower sintering temperature at 1465℃ and short sintering time. The mechanical properties of sintered tungsten heavy alloy are found to be mainly dependent on the particles size of raw tungsten powders and liquid-phase sintering temperature.     

Mapping the compaction and sintering response of tungsten-based materials into the nanoscale size range

Considerable knowledge exists on processing tungsten powders over a broad particle size range. Published data and processing models have been combined for tungsten powders ranging from 20 nm to 18 μm to build a response model for press-sinter processing. The model predicts apparent density, green density, green strength, sintered density, sintered grain size, and product properties such as strength, hardness, and wear resistance. Further, the model isolates several problems as particle size decreases that will require changes in how tungsten powders are handled, compacted, and sintered. Maps of strength versus processing conditions are generated from the model to direct future efforts toward improved properties using nanoscale tungsten powders. From these findings, new opportunities become evident for press-sinter consolidation of nanoscale powders.     

Characterization of nanometer tungsten powders

Three types of tungsten powders were prepared by hydrogen reduction of three precursor powders at low temperature,which were used as samples,and were then characterized by Brunauer-Emmer-Teller (BET) method,scanning electron microscopy (SEM),transmission electronic microscopy (TEM),small angle X-ray scattering (SAXS),and field-emission scanning electron microscopy (FESEM) respectively.The results showed that although BET and SEM could not characterize the particle size of nanometer powders,they were important means of assistance to exclude non-nanometer powders.TEM and FESEM could directly measure the particle size of nanometer powders,but this needs a lot of time,to count the average particle size and particle size distribution.SAXS could not describe the state of agglomeration.By the combination of FESEM and SAXS,the particle size,particle size distribution,and particle shape of nanorneter powders could be preciscly characterized.     

高能球磨法制备纳米晶Ni粉的研究

采用高能球磨法制备出了纳米晶镍粉,并利用X射线衍射仪（XRD）、扫描电镜（SEM）、透射电镜（TEM）等分析检测手段,研究了该纳米晶镍粉末的结构、形貌和相的变化。结果表明,镍粉末平均粒度和晶粒度随球磨时间增加不断减小,而应变随球磨时间增加不断增大;当高能球磨54h后,球磨产物为FCC结构的鳞片状多晶体,晶粒度为17nm左右,应变为0.48%,颗粒尺寸为150～200nm;球磨时间增加至98h,产物中出现非晶相,但仍以多晶为主,晶粒尺寸为7nm,应变为1.24%,粉末团聚严重。     

A facile pathway to prepare ultrafine WC powder via a carbothermic pre-reduction followed by carbonization with CH4-H2 mixed gases

In the present work, ultrafine tungsten carbide (WC) powder with a high purity has been prepared by first roasting yellow tungsten trioxide (WO₃) and carbon black powder under argon atmosphere followed by the further carbonization reaction with CH₄-H₂ mixed gases. The effects of C/WO₃ molar ratio, CH₄ percentage in the CH₄-H₂ mixed gases on the phase composition, morphology and particle size of the products were discussed. The results revealed that when the C/WO₃ molar ratios were 2.5 and 2.6, nano tungsten carbide powder with the average particle sizes of 93 nm and 77 nm could be prepared. Whereas, when the C/WO₃ molar ratio was in the range of 2.7–3.5, the finally prepared WC has the particle size of 446–192 nm, and became smaller with the increase of C/WO₃ molar ratio. The percentage of CH₄ should be <15% to prepare WC with a low free carbon content. From the results of thermodynamic calculation, X-ray diffraction (XRD), FE-SEM, and infrared carbon‑sulfur analyzer, it was concluded that ultrafine tungsten carbide powders with a high purity could be successfully prepared by this method.     

纳米钨粉粒度分布的表征研究

采用X射线小角散射法（SAXS）和光子相关谱法（PCS）测试了纳米钨（W）粉的粒度分布。结果表明,采用SAXS测试出的纳米W粉的粒度分布与透射电镜观察和比表面积法测试结果十分接近,能较为准确地表征纳米W粉的一次颗粒的粒度分布;但为了得到可信的结果,所选择的X射线衍射仪的最小可测试角必须足够小。PCS法测试的纳米W粉的粒度随分散条件的变化而变化,所提供的最佳分散条件可用于测定二次颗粒的粒度分布。     

Vacuum sintering of WC-8 wt.% Co hardmetals from WC powders with different dispersity

The effect of sintering temperature and particle size of tungsten carbide WC on phase composition, density and microstructure of hardmetals WC-8 wt.% Co has been studied using X-ray diffraction, scanning electron microscopy and density measurements. The sintering temperature has been varied in the range from 800 to 1600 °C. The coarse-grained WC powder with an average particle size of 6 μm, submicrocrystalline WC powder with an average particle size of 150 nm and two nanocrystalline WC powders with average sizes of particles 60 and 20 nm produced by a plasma-chemical synthesis and high-energy ball milling, respectively, have been used for synthesis of hardmetals. It is established that ternary Co₆W₆C carbide phase is the first to form as a result of sintering of the starting powder mixture. At sintering temperature of 1100-1300 °C, this phase reacts with carbon to form Co₃W₃C phase. A cubic solid solution of tungsten carbide in cobalt, β-Co(WC), is formed along with ternary carbide phases at sintering temperature above 1000 °C. Dependences of density and microhardness of sintering hardmetals on sintering temperature are found. The use of nanocrystalline WC powders is shown to reduce the optimal sintering temperature of the WC-Co hardmetals by about 100 °C.